SF6 ground-based infrared solar absorption measurements:: long-term trend, pollution events, and a search for SF5CF3 absorption

Infrared solar spectra recorded with the Fourier transform spectrometer in the McMath solar telescope complex on Kitt Peak (31.9degreesN latitude, 111.6degreesW, 2.09 km altitude), southwest of Tucson, Arizona, have been analyzed to retrieve average SF6 tropospheric mixing ratios over a two-decade time span. The analysis is based primarily on spectral fits to absorption by the intense, unresolved nu(3) band Q branch at 947.9 cm(-1). A best fit to measurements recorded with SF6 near typical background concentrations yields a SF6 increase in the average tropospheric mixing ratio from 1.13 pptv (10(-12) per unit volume) in March 1982 to 3.77 pptv in March 2002. The long-term increase by a factor of 3.34 over the time span is consistent with the rapid growth of surface mixing ratios measured in situ at Northern Hemisphere remote stations, though the infrared measurements show a large scatter. Average tropospheric mixing ratio enhancements above background by 2-3 orders of magnitude have been identified in spectra recorded on 5 days between November 1988 and April 1997. These spectra were individually analyzed in an attempt to detect the strongest 8-12 mum band of SF5CF3, a molecule recently identified with an atmospheric growth that has closely paralleled the rise in SF6 during the past three decades. Absorption by the strongest SF5CF3 band was predicted to be above the noise level in the Kitt Peak spectrum with the highest average mean tropospheric SF6 mixing ratio, assuming the reported atmospheric SF5CF3/SF6 ratio and a room temperature absorption cross sections reported for the SF5CF3 903-cm(-1) band. An upper limit of 8 x 10(15) molecules cm(-2) for the SF5CF3 total column was estimated for this case. We hypothesize that the highly elevated SF6 levels above Kitt Peak resulted from a local release experiment rather than production via electrochemical fluoridation of intermediate products, the proposed source of atmospheric SF5CF3. The absence of the SF5CF3 feature in the spectra with elevated SF6 is consistent with the absence of SF5CF3 reported in a pure SF6 sample. Published by Elsevier Science Ltd.